Catalytic treatment of hydrocarbons



which proceed concurrently Patented Jan. 18, 1944 -CATALYTIC TREATMENT OF HYDRO- cannons Charles L. Thomasand Joseph D. Danforth, 0111- I cago, Ill., assignors to Universal Oil Products Company, Chicago, lll., a corporation of Delaware No Drawing. "Application November 12,1940;

Serial No. 365,258

I 8Clai ms. (01. 196-52) 312,845, filed January 8, 1940. the mixing of This invention relates to a process for thecon-' versionof hydrocarbons; such as petroleum fractions and hydrocarbon oils generally, in the presence. of catalysts to produce substantial yields of hydrocarbons within the gasoline boiling range and having high antiknock value. The process maybe applied to. conversion involving low boiling as well as high boiling hydrocarbons whether they are of synthetic or'natural origin, or are produced as for example from primary distillate resulting from the destructive distillation'of hy drocarbon-containing materials such as coals, lignites and shales. v

It has been found in connection with synthetic cracking catalysts consisting of hydrated silica activated by various hydrous oxides such as hydrated alumina,'hydrated zirconia, thoria; etc., thatapproximately 10-60% of inert or mildly active refractory'materials such asclays, forexample, may be introduced into the catalytic material to reduce the cost while only reducing the activity of the catalyst to a small extent. Ac-

- cording to the "practice of the present invention a catalyst of this type is used which has added.

thereto a component which offsets this lossof activity and in some cases gives increased activboric oxide has been disclosed with this type of 'crackingcatalyst which, however," has not been mixed with a refractory support'and has been impregnated in a different manner. In the present invention, improved results have been obtained because-the boric oxide is deposited by new methods upon the supported silica-alumina catalyst and as a result thereof, the catalyst can be prepared at alower cost, it has a longer-life,

' and higher temperatures and shorter time-can be used when regenerating the catalyst. The refractory supports-which maybe employed are relatively numerous and there are a; number of methods which may be employed in preparing "the mixtures of. hydrous oxides upon which a 'boron compound is subsequently deposited to yield boric oxide.

, The refractory supporting materials employed include powdered diatomaceous earth, kaolin,

China. clay, pumice, sand, carborundum, quartz,

fine powders oi alumina, zirconia, thoria, titania,

chromite, rutile, llmenite, zircon, bauxite, etc.

ity'over the original catalyst. In addition to this, v

the use of thepreferred catalyst brings about a reduction of the gas and carbon forming reactions l or incidentally to thegasoline-forming reactions.

Many of these materials may have catalytic properties in various chemical reactions and some of them influence hydrocarbon cracking reactions.

It is of particular importance to note, however, that all of these materials have no activity or relatively small activity as compared with the In one specific embodiment the present iuvention comprises subjecting hydrocarbon oil under conditions of temperature, pressure and time adequate'to produce a substantial yield of high antiknock gasoline to contact with granular'particles of a synthetically prepared composite of hydrated silica and hydrated alumina associated with a refractory support, said particles having boric oxide impregnated thereon.

According to the, invention, hydrocarbon oils more generally of a distillate character are catalytically cracked in the presence of particles of synthetic cracking catalysts intimately mixed with refractory supports which are then further activated by boric oxide deposited in and on the active surfaces. The hydrous oxide catalysts deposited upon the refractory supports consist preierably of a mixture of hydrated silicon dioxide and hydrated alumina and/orzircom'a prepared by special methods so as to eliminate alkali metal impurities. Thoria, magnesia, vanadia and other oxidesmay also besimilarly added but not with equivalent results. In the pending application of, one of the inventors, United States SerialNo.

specially prepared catalysts useful in this invention. The supports are of-value only in so far as they are refractory materials which will not fuse'or sinter when exposed to high temperature conditions inperiodic use and regeneration. When one of these materials having the greatest amount of activity and another having no sotivity in influencing hydrocarbon reactions are used assupports under corresponding conditions, no substantial diiference is reflected in the activity of the supported catalytic materials. The amount-of the support used may be up to or more by weight 'of'the completed catalytic material. The smaller the particle size of the support, the more suitable it may be considered because of the more extended distribution throughout the catalyst. Although the powdered support may be added to the catalyst gel during. some stage of its preparation as for" example when thesilica gel is precipitated, it may be preferable to intimately mix the'finely divided support with the washed'or purified catalyst gel, thus reducing. the amount of material to be handled and washed; in the preparation of the gel. Alternatively, but not'with equivalent results, the dried catalyst gel may be mixed with the powsilica by hydrolysis,

. to remove these secutively precipitated. According to one general method of preparation, the hydrated silica may be precipitated from a dilute solution of commercial water glass, and subsequently mixed with the remaining hydrous oxide components.-

The mixing may be accomplished for example,

by suspending the hydrated silica precipitated upon the refractory support in a solution of a metal salt and then precipitating the hydrous oxideof the corresponding metal in the presence of the suspended hydrated supported silica by the addition of a suitable alkaline precipitant. Various other procedures may be followed wherein these components may be co-precipitated in the presence of the refractory. support or separately precipitated and the components intimately mixed. The supported hydrated silica may for example, be heatedin asolution of a metal salt, and the corresponding metal hydrousoxide deposited in the presence of the supported hydrated or the said silica may be mixed with a relatively concentrated solution of a metal salt to form.a paste which is then heated todeposit the desired metal oxide.

In; the manufacture of refractory synthetic catalysts it has been found necessary where sodium compounds have been included in the catalyticmaterial during preparation, to treat the materialat some stageof its preparation in order alkali metal impurities. This may be accomplished by washing with various acidic or salt solutions such as solutions of ammonium salts of strong acids, or of salts of the metals of the hydrous oxides used. This is illustrated in the specific examples given below.

The composite gel which is usually recovered as a filter cake may 7 then admixed with a lubricant to facilitate adhesion of the particles and prevent adhering or stickingin the briquetting or pilling machines used in forming the material into pellets, pills or other consolidated and shaped particles. Varlousother methods are also available for making granular particles such as drying a uniform slurry in thin layers so as to shrink and crack into granules -of graduated mesh. The.

particles may then be calcined at temperatures of the order of l000-1600 F., more or less. Whatsoever the method of compositing the hydrous oxides constituting the preferred cracking catalysts, and mixing them with-the refractory support, and whatsoever the subsequent procedures used to consolidate or form into granular particles, these particles may be improved in their catalytic properties according to the following procedures although not necessarily with exactly equivalent results. I

Calcined supported synthetic cracking catalysts are impregnated with a solution. of a suitable boron compound or a suitable liquid boron compound. Compoundswhich may be used are boric acid and organic borates, for example, or other boron compounds which will form boric oxide upon decomposition. The dried silica-alumina and/or zirconia catalyst may be dipped, im-

. catalyst surfaces may liquid and deposit glycol may also the catalyst generally or tri-amyl borate may be absorbed upon a synthetically prepared cracking catalyst which is subsequently heated or ignitedto remove the boric oxide in and on the surfaces of the cracking catalyst. A large number of organic compounds may be used such as dibutyl borate, triethyl boron, boron trimethyl, fluo-boric acid, etc., either as liquids or in organic solvents. Similarly, boric acid may be used and any suitable solvent may be employed. Alcoholic solutions are particularly desirable but the practice is not restricted thereto since glycerine has been employed with good results. Other polyhydroxy alcohols such as ethylene be used as well as triethanol amine. Theconcentration of boric oxideon the be controlled by varying the concentration and amount of the solutions of the boron compound used,or the number of impregnating treatments. In the formation of the boric oxide on the catalyst surfaces, the impregnated boron compound may be decomposed in any desired manner. In the case of triamyl borate the catalyst may be ignited or it may be hydrolyzed in a current of moist air for example, the ignition procedure being preferable. Catalysts prepared in this manner containing approximately 2 to .,8% of boric oxide by weight of give good'results but higher proportions of the boric oxide up to 15% or more may be employed.

Various types of hydrocarbon conversion reactions take place in the presence of the catalyst depending partly upon the temperature, pressure he extruded or may be dried and 7 may occur whereby and time conditions and partly upon the nature of th hydrocarbon oil processed. These reactions may include carbon-to-carbon cleavage, isomerization, cyclizatlon, drogenation and desulfurization reactions. In the case of higher boilinghydrocarbons, for example there is a cleavage of long-chained carbon-to-carbon bonds. Isomerization reactions the lower boiling hydrocarbons formed tend to become more branch chained.

' Also'hydroaromatic hydrocarbons present in the oil undergoing decomposition or formed therein by cyclizatlon of olefins may undergo dehydrogenation to form aromatic hydrocarbons and hydrogen liberated in these reactions may combine with other oleflns present during reaction to form parafiinic hydrocarbons. The later reactions tend to occur at the lower temperatures given in the range of operating conditions where- I as more unsaturated hydrocarbons, particularly olefins are produced at the higher temperatures employed. The hydrocarbons produced are, generally ofv a more branched chain structure than are those produced in thermal cracking treatment. The temperature employed may be a temperature from about 750 F. to about 1100 F. and the pressure employed may be from about atmospheric' to about 500 pounds per square inch. The space velocities employed may vary from to 60, the space velocity being defined as the hourly volume of liquid hydrocarbon charged per volume of reactor space occupied by the catalyst.

The catalysts may be conveniently utilized in carrying out various types of hydrocarbon condehydrogenation, hy-

' change devices.

version reactions" when employed as filling {naterial in tubes or they may be disposed in trays Orin chambers; The average size of the particles may vary within the approximate range of (to 10 mesh more or less which is not restricted to any particular shape or method or particle'fformation. A hydrocarbon oil fraction 'may be heated to substantially reaction temperature and the vapors contacted with thestationary catalyst masses. The hydrocarbon vapors may be passed downward through the catalyst, and where large beds of catalyst are involved the passage of vapors may be restricted to definite paths rather than allowing theyapors to have unrestricted contact with thelarge beds of catalyticmaterial. Where this method is used, the temperature of the contact materials while in use and during regeneration may be controlled" by charging stock in producing the gasoline 'prod- Hot. The proces however, is riot'restricted t the use or thecatalyst as granular-masses disposed as fixed-beds in catalytic reactors, since the catalytic material may beimpregnated when in the dried powder condition and the impres nated powdered material subsequently mixed'with a stream oi'hydrocarbon oil to be processed and then subjected to condition 01' time, temperature and pressure adequate to produce substantial yields 01' high antiknock gasoline.

The following specific examples are given to illustrate specific applicatlonsoi' the process or the invention, the method of catalyst preparation also being indicated. The invention should not be considered as limited to these examples of the process orto' the particular catalyst preparation since these are given merely as illustrations of the novelty and utility of the invention. I

Example I A catalyst having the approximate composition of 100S1Oai5A12Oai5B2Oa and containing 50% by weight of kaolin is prepared as follows: A commercial sample 01 water glass of approximately 41 Baum gravity and containing approximately 28.5% 810: and 8.9% NazO is diluted approximately times with water containing in suspension finely divided kaolin passing a 300 mesh screen. Hydrochloric acid is added to the water glass solution while agitating thoroughly and a precipitate begins to form and remains in suspension in the alkaline solution. The addition of acid is continued until there is an excess or acid, the pH being approximately 3. The excess acid may then be substantially neutralized by the addition or ammonium hydroxide whereupon the hydrated silica is practically all precipitated. The hydrated silica is filtered and washed with water acidulated with hydrochloric acid until the precipitate is substantially free from sodium. The purified hydrated silica is suspended in an aluminum chloride solution inan amount suitable to form catalyst oi the above composition. and hydrated aluminapreclpitated inthe presence of the suspended hydratedsilica by the addition or ammonium hydroxide. The

. composite precipitate'is filtered and the filter cake is washed with water andd'ried at approximately'200-250 F. a The dried material is then mixed with a small amount'oI hydrogenated vegetable'oil lubricant and formed into pelleted particles 01%;" x size in 'a pilling machine.

The material is then calcined at a temperature of approximately 1500? F. for one hour. After cooling, the calcined material is impregnated with an alcoholic solution of boric acid in sufllcient amount to deposit'approximately 5'mols of 1320:

per -100'mols of 810: on the catalyst. The boric oxide is deposited by heating to'distill out andre- "cover 5 the methyl alcoholxthereupon depositing reactor heated to a temperature 01' mately 932 F. and

the boric oxide in and on the surfaces'ot the supported silica-alumina catalyst.

Catalyst as above described is disposed'in a a Pennsylvania gas oil is "vaporized and preheated to approximately the same temperature and directedthrough the catalyst at substantially atmospheric pressure. The volume per cent yield of gasoline is 30.2% as compared to 27.7 volumeper'cent of gasoline' which is obtained when processing under the same conditions and using the same catalyst with the water glass used. of sodium v to the water glass solution containing finely divided kaolin before-the addition of hydrochloric omission of the boric oxide according to the motor method, v 7 Example 11 A catalyst having approximately the samecomposition as the catalyst or Example I is similarly prepared except that of the weight of chloride is added acid. As a result of theaddition of the sodium chloride a very finely divided precipitate is deposited upon thefinely divided kaolin as contrasted withthe gelatinous of air.

formed in Example I. The catalyst .is, then purified to remove alkali metal impurities similarly as in Example I'andthe hydrated alumina deposit upon the hydrated silica. The finely divided materialis dried and impregnated with the boric oxide without forming into granular particles.

Catalyst prepared in the above manner is mixed to the extent of 1% by weight with a "Pennsylvania gas oil 01' approximately-a 36 A. P.'I. gravity and heatedto a temperature of approximately 975 F. and directed to a reaction chamber at an average temperature of approximately 815 F. at a pressure oi approximately 50 pounds per square inch. A volume per cent oi 400 F. endpoint gasoline having 76 octane number is obtained in asingle pass. The spent catalyst is separated from non-vaporous residue It is then filtered to remove most of the nonvaporous oil residue and ignited at a tempera- F. in the presence ture of approximately 1200" Catalysts regenerated in this manner gage substantially the same gasoline yield as a ve.

Example II! A catalyst having the approximate composition of IOOSiOliQOZl'O2I5B20: and containing 50% by weight of kaolin is prepared as follows: similarly as the cat- This catalyst is prepared approxiprecipitate that is yield of approximately 38 removed Iromthe process.

alyst in Example I except that the nnely divided kaolin is not mixed in the. water glass solutionbutis added to the gel composite. before drying. The hydrated silica is precipitated and washed substantially free from; sodium andthen suspended in a zirconyl chloride solution in an amountsuitable to form catalyst of the above composition. Hydrated zirconia is then precipitated inthe presence of the suspended hydrated silica by the addition of ammonium hydroxide. The composite precipitate is filtered and the filter cake is water washed and intimately mixed with the finely divided kaolin. The mixture is then extruded through a quarter-inch dle and the extruded material'cut intoquarterinch sections.. The extruded particles are dried at approximately 200-250 F. and the dried material is calcined, at a temperature of approxiand recover the methyialcohoi, thereupon depositing the boric oxide in and on the surfaces of the supported silica alumina catalyst.

Catalysts as described above when disposed in a reactor and contacted with vapors of a Mid-Continent gas-oil at a temperature of approximately 900 F. using a space velocity of approximately 4 and apressure of approximately 40 pounds per square inch'give ayield of approximately 35 volume per cent of 400 end-point gasoline having an octane number of approxi mately 78 by the motor method. 7 a

We claim as our invention:

1. A process fortheconversion of hydrocarbons to produce a substantial yield of high antiknock gasoline therefrom which comprises subjecting said hydrocarbons at a temperature of from about 750 to about 1100 F. at a pressure of from aboutatmospheric to about 500 pounds per square inch and a space velocity of from about Vi to about 60 to contact with-a calcined supported silica-zirconia catalyst said composite having been impregnated with boric oxide subsequent to the calcination thereof.

,resulting from compositing assasoa for the conversion or hydrocaryield of high antiknock gasoline therefrom which comprises sub- 2. A process iecting said hydrocarbons at a temperature of from about 750 to about 1100 F. at a pressure of from square about atmospheric to about 500 pounds per to about 60 to contact with a cracking catalyst precipitated hydrated silica. precipitatedhydrated zirconia and a finely divided refractory support. drying, calcining and I impregnating said calcined material with boric oxide.

3. A catalyst for use in hydrocarbon conversion reactions resulting iron} the calcination of a composite comprising a hydrated silica, a hydrated zirconia and a relatively inactive support, said composite having been impregnated with boric acid subsequent to the calcination thereof.

Y 4. The catalyst defined in claim 3 further characterized in that it contains hydrated alumina.

5. A process forthe conversion or hydrocarbons which; comprises contacting the hydrocarbons under catalyticcracking conditions with a calcined composite comprising a hydrated silica and a hydrated zirconia, said composite having been impregnated with boric oxide subsequent to the calcination thereof.

6. The process of claim 5 further characterised in that the catalyst contains alumina.

- 7. A process for the conversion 01' hydrocarbons which comprises contacting the hydrocarbon under catalytic cracking conditions with a calcined composite comprising silica, zirconia and a refractory supporting material of. relatively lowcatalytic activity, said composite having been impregnated with boric oxide subsequent to the calcinati'on thereof.

8. A process for the conversion 0! hydrocarbons which comprises contacting the hydrocarbon under catalytic cracking conditions with a" calcined composite comprising silica, zirconia, alumina and a refractory supporting material of relatively low catalytic activity. said composite having been impregnated with boric oxide subsequent to the cal-- cination thereof. v

; i CHARIEB L. THOMAS.

JOSEPH D. DArIFOR'I'H.

inch and a space velocity of from about. 

